Reversible dental adhesive

ABSTRACT

A method of removing a dental adhesive may comprise locating the position of the dental adhesive, directing radiant energy into the dental adhesive causing the dental adhesive to weaken a bond formed with the dental adhesive, and breaking the bond by applying a suitable force to overcome the weakened bond. A dental adhesive may comprise a polymer and a dye or pigment, The dental adhesive may be formulated to cure to form a bond that is weakened in response to the dye or pigment absorbing radiant energy subsequent to curing.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.61/683,716, filed Aug. 16, 2012, and U.S. Provisional Application No.61/800,372, filed on Mar. 15, 2013, the disclosure of each of which isincorporated herein by reference in its entirety.

TECHNICAL FIELD

The present disclosure relates to dental adhesives. In particular, thepresent disclosure relates to dental adhesives that are reversible orotherwise able to break the adhesive bond when the bond is no longerdesired.

BACKGROUND OF THE INVENTION

In the contemporary dental office many types of adhesives, composites,cements, and other restorative resin systems are utilized daily. Most ofthese resin systems are designed to permanently repair or set into placea prefabricated prosthetic. Once placed, these restorative prostheticsmust be busted/broken to be removed at a later time due to the fact theadhesive bond will not allow removal of the restorative prosthetic.

What is needed in the art are dental resin systems that are reversible,such that they can be purposefully destabilized and removed withoutbreaking the prosthetic.

SUMMARY

A method of removing a dental adhesive may comprise locating theposition of the dental adhesive, directing radiant energy into thedental adhesive causing the dental adhesive to weaken a bond formed withthe dental adhesive, and breaking the bond by applying a suitable forceto overcome the weakened bond.

A dental adhesive may comprise a polymer and a dye or pigment, Thedental adhesive may be formulated to cure to form a bond that isweakened in response to the dye or pigment absorbing radiant energysubsequent to curing.

DETAILED DESCRIPTION

The present invention may be embodied in other specific forms withoutdeparting from its spirit or essential characteristics. The describedembodiments are to be considered in all respects only as illustrativeand not restrictive. The scope of the invention is, therefore, indicatedby the appended claims rather than by the foregoing description. Allchanges which come within the meaning and range of equivalency of theclaims are to be embraced within their scope.

Example embodiments of the present invention include light curable orchemical curable materials to create an adhesive or adhesive system thatis reversible in adhesive nature. In particular, embodiments of thepresent invention include adhesives that once cured form a strong bond.However, by introducing additional energy into the cured adhesive, thecured adhesive becomes degraded, destabilized and/or depolymerized suchthat the adhesive nature of the cured adhesive is reversed, allowingrelease of the bond.

Example embodiments of the present invention utilize light and chemicalcurable monomer/polymers to create a polymerizable resin or adhesivesystem that is reversibly destabilized/de-polymerized and or molten intoa temporary or nontemporary degraded/weakened state.

In one example embodiment, a method of destabilization includesintroducing laser energy that directly and precisely transfers energy tothe polymerized resin wherein it is absorbed and turned into heat. Theheat in turn causes the polymerized resin to undergo de-polymerization,degradation or simply melts the polymerized matrix sufficiently that itbecomes weakened or enters a fluid state. In alternative embodiments,other methods of introducing energy can be used, for example heatblowers, heat elements, or other similar methods.

Once the resin system is in a weakened or molten state any dentalprosthetic or appliance can be removed without applying excessive forcethat could break or alter said prosthetic or appliance. For example,once the adhesive system has absorbed a sufficient amount of energy, theadhesive properties of the systems are weakened to the point that adental professional could easily remove the dental prosthetic.

One example of a reversible resin includes are monomers that formhomopolymers without branching or cross-linking. The ideal monomer wouldconsist of a light and chemical curable monomer that when polymerizedforms a thermoplastic that melts at low temperature, preferably between40C and 70C. Another example of reversible resins are monomers that arecapable of de-polymerization and degradation when subjected to elevatedtemperatures, preferably between 40C-70C. Additional reversible resinsare also contemplated such as light and chemical curable polymerscapable of crosslinking/branching and co-polymerization, polymerization,such that they retain the ability to degrade, de-polymerize and/or meltat an appropriate temperature.

In the laboratory we have found a unique means to weaken/degrade apolymer incorporating plasticizers. The system comprises a monomer(s), acuring agent, a radiant energy absorbent pigment/dye and aplasticizer(s). When incorporated into a light curable formulation wecould create a reversible polymeric system. The liquid formulation whenirradiated with the appropriate light would initiate polymerization andform the expected rigid polymer matrix. The plasticizer(s) can be addedin amounts that can vary the rigidity and flexibility of the polymer.

When the cured polymer is irradiated with a laser attuned to the radiantenergy dye/pigment the light is absorbed and converted into heat thatbegins to heat the polymer matrix locally. The plasticizer becomesheated and expands and stresses the polymeric confinement such that iteventually begins to crack/break (stress propagation) the polymericcrystalline matrix on a microscopic level. The polymer when heatedbecomes permanently weakened and is easily fractured by the addition ofexternal forces such as bending/flexing the polymer. Rapid heating ofthe polymer actually fractures the polymer such that the polymer breaksapart or forms a snowflake type fractures in the polymer.

The plasticizer may perform multiple functions within the polymericmatrix. First, when plasticizer becomes heated it becomes either moltenor in a more fluidic state which acts as a lubricant and/or solvent suchthat it is more capable of reducing friction within the polymericnetwork; therefore the polymer becomes more pliable. Second, theplasticizer expands and applies internal pressure inside the polymericmatrix stressing the bonds making them weaker. If sufficient heat isapplied the expansion becomes great enough to actually sever those bondsand the polymer begins to fracture into a permanently weakened state.

The laser and absorbent dye and pigment are only a means to communicateheat to the plasticized polymeric matrix, other means of adding heat tosaid polymer are also possible, such as a heated wand or bag that isplaced over the polymer and heated through conduction. A heat lamp wouldalso deliver the required heat; in effect any device capable ofdelivering heat to the polymer would complete the system.

Suitable plasticizers include but are not limited to: dibutyl phthalate,triethyl citrate, triacetin, sucrose diacetate hexa-isobutyrate and anyother useful plasticizer.

Chemical cure resin systems are mixed composition systems. Usuallyincorporates a part A and a part B, that when mixed together uniting thepolymerization catalyst results in subsequent polymerization.

Light cure resin systems are light sensitive compositions that containcatalysts that initiate polymerization upon receiving radiant energysuch as light.

The preferred types of resins are acrylics/methacrylics because they arecompatible with almost all contemporary dental resin systems currentlyon the market.

Resins such as epoxy, urethanes and other useful resins are alsocontemplated.

Useful acrylic resins are polyethylene glycol methacrylates,polypropylene glycol methacrylates, Diurethane dimethacrylate,hydroxyethyl methacrylate, bisphenol A diglycidyl dimethacrylate,triethylenegycol dimethacrylate, isodecyl methacrylate, Bisphenol Aethoxylate dimethacrylates, Poly(ethylene glycol) methyl ethermethacrylate, and many other useful methacrylic resins.

Light cure systems incorporate a tertiary amine such as dimethylaminoethyl methacrylate and a photo initiator such as camphorquinone.

Chemical cure systems usually consist of benzoyl peroxide in part A, anddimethyl para toluidine in part B, that when mixed together initiatefree radical polymerization.

Absorption dyes are designed to significantly absorb at knownfrequencies/wavelengths. These dyes are classified by their specificfrequencies where their maximum absorption or lamda maximum isdetermined Many absorption dyes have multiple Lamda Max. Absorption dyesin raw material form come in many colors covering much of the colorspectrum. In many applications the physical color of the raw dye is notan issue, since the application is indifferent. There are someapplications where colors are very important and the selection isimperative to the system. As an example, dental restorative resinsystems are designed to replace or cement missing portions of a tooth orteeth. A red or blue tinted resin would not be aesthetically pleasing tothe patient as it would be obvious to strangers, since it is generallyaccepted that teeth should be shades of white.

This patent utilizes specific dyes, and resin systems to create anaesthetically pleasing resin/monomer/polymer system that is capable ofsignificant absorption of radiant energy at specific wavelengths.

More specifically the present invention targets wavelengths in ranges of380 nm-450 nm More broad ranges of 400 nm-615 nm. Most broad ranges of100 nm-700 nm.

The ideal wavelength is about 405 nm, or any radiant energy sourcecapable of producing visible violet light. Less ideal are radiant energysources that produce UV, blue and green light; though are definitelywithin the scope of this patent. The physical color of raw absorptiondyes usually counter-correspond to the wavelengths of the radiant lightsource. Blue light is usually absorbed by yellow dyes. Green light isusually absorbed by red dyes. UV light is usually absorbed by white totransparent dyes. Violet light is usually absorbed by yellow, white, andtranslucent dyes.

Violet light is ideal, because the corresponding absorption dyes are themost aesthetically adaptable into a resin system. The best to worstcolors for dyes/pigments are:

Translucent/transparent/clear

White

Off white

Light yellow

Dark yellow

Light brown

Dark brown

All other colors such as blues, greens and reds are very difficult tomake aesthetically pleasing; it requires great skill to add additionalcolors to offset these primary colors; such as adding red and greentogether to produce a more useful color like brown.

The absorption dyes associated with UV light are as ideal as those forviolet light; namely translucent/transparent, white dyes. UV light issecond to violet light only because in some cases UV light isphysiologically hazardous and extra precautions must be in place for itsuse.

The preferred light of the present invention is violet light having awavelength range of about 380 nm-450 nm. The 405 nm laser is an idealradiant energy device of the present invention. More specifically, the405 nm diode laser is preferred since its cost and compact size combineto create a more affordable laser.

Violet light is preferred because of its capability to match radiantenergy absorbent dyes of aesthetic colors most preferably transparent,translucent, and or white in physical color. There are multiplewhite/translucent dyes or pigments that absorb violet light such as:4,4″-(1,2-ethenediyl)bis-1,1′-biphenyl, and4,4′″-bis[(2-butyloctyl)oxy]-1,1′:4′,1″:4″,1′″- quaterphenyl and2-[1,1′-biphenyl]-4-yl-6-phenyl-benzoxazole and3,5,3″″′,5″″′-tetra-t-butyl-p-sexiphenyl and2-(1-naphthyl)-5-phenyl-oxazole and 3,5,3 . . . ,5 . . .-tetra-t-butyl-p-quinquephenyl and any other useful dyes or pigmentscapable of absorbing violet light.

Dyes and pigments that are physically yellow also absorb violet lightsuch as:2,2″-([1,1′-biphenyl]-4.4′-diyldi-2,1-ethenediyl)bis-benzenesulfonicacid disodium salt and/or any other dye or pigment capable of absorbingviolet light.

Many white/translucent/crystalline dyes and pigments are also absorbedby UV light, these dyes are also very capable of creating an aestheticresin system; many dyes and pigments listed above will also absorb UVlight. Since UV light may present a physiological hazard it is not aspreferred as violet light.

There are many radiant energy absorbent yellow dyes and pigments thatabsorb blue light. Therefore blue light is an excellent radiant energysource to irradiated aesthetic resin systems containing yellow dyes.Yellow dyes are not as good as white/translucent/crystalline dyes andpigments, but are still capable of creating an aesthetic resin system.

There are some violet light absorbent dyes that are slightly yellowand/or light yellow in physical color whose absorbance efficiencyexceeds about 70%. Dyes that are highly light absorbent at a desiredwavelength are preferred over those that have less light absorbency,because you need to add less dye to the formulation for an equal effect;regardless of the physical color of the dye. It is much easier to makean aesthetic resin composition with a highly absorbent dye since itrequires a smaller quantity of dye in the first place; the ideal highlylight absorbent dye would require such a small amount of dye that thecolor change in the resin composition would be insignificant.

Violet light absorbent dyes that are yellow in physical color and absorbgreater than about 70% light are ideal dyes for manufacturingclear/transparent/white aesthetic resin compositions.

The absorbance characteristics of all dyes can be selected to impart adesired absorption effect. The absorbance effect can be adjusted betweenlocalized and diffuse characteristics. For a localized effect the highlyradiant energy absorbent dye is selected such that most of theabsorbance is concentrated at the surface and very little is transmittedinto deeper layers. This is beneficial when you want radiant energylimited to the surface or near surface and want to avoid transmission tosubstrates that lie underneath. The same localized effect can bemanufactured by low absorptive dyes as well; simply by adding more dyeto the formulation to compensate for the lack of absorption, this is notpreferred because it is more difficult to make an aesthetic composition;unless the dye is of the appropriate color to begin with.

For a diffuse effect a highly absorptive radiant energy dye(s) can beadded in ever-smaller quantities to a point that the spaces between thedyes(s) become great enough to allow the desired diffusion of radiantenergy. Alternatively, a low radiant energy absorptive dye(s) can alsobe selected to produce a customized composition that allows light topass into deeper layers (sub-surface) of the composition and intosubstrates underneath if desired.

These radiant energy absorbent dyes and pigments are dissolved, mixed,and/or blended together with monomer(s) and/or Co-monomer(s) to create alight absorbent resin system. Additional catalysts, initiators andphotoinitiators are added to the resin formulation to create apolymerizable radiant energy absorbent resin matrix/system; such thatwhen polymerization is initialized by chemical, photochemical and orthermal means, it forms into a hardened physical state.

In both the monomeric state and the polymeric state the formulation iscapable of absorbing radiant energy of a specific wavelength in order toeffectuate a change within the formulation itself, such as thermal,chemical, chemical reactions, and/or physical or material changes ormodifications. An example of such use is a radiant energy absorbent dyedissolved into a polymerizable monomer system that is polymerized into ahardened state photochemically; the polymerized polymer is thenirradiated with sufficient radiant energy of the wavelength that matchesthe incorporated dye thereby heating the polymer sufficiently that iteither heats, fractures, cracks, melts or becomes permanently ortemporarily weakened. Many uses are possible with different systemsdependent on the desired outcome.

Chemical cure resin systems are mixed composition systems. Usuallyincorporates a part A and a part B, that when mixed together uniting thepolymerization catalyst results in subsequent polymerization.

Light cure resin systems are light sensitive compositions that containcatalysts that initiate polymerization upon receiving radiant energysuch as light.

The preferred types of resins are acrylics/methacrylics because they arecompatible with almost all contemporary dental resin systems currentlyon the market.

Resins such as epoxy, urethanes and other useful resins are alsocontemplated.

Useful acrylic resins are polyethylene glycol methacrylates,polypropylene glycol methacrylates, Diurethane dimethacrylate,hydroxyethyl methacrylate, bisphenol A diglycidyl dimethacrylate,triethylenegycol dimethacrylate, isodecyl methacrylate, Bisphenol Aethoxylate dimethacrylates, Poly(ethylene glycol) methyl ethermethacrylate, and many other useful methacrylic resins.

Light cure systems incorporate a tertiary amine such as dimethylaminoethyl methacrylate and a photo initiator such as camphorquinone.

Chemical cure systems usually consist of benzoyl peroxide in part A, anddimethyl para toluidine in part B, that when mixed together initiatefree radical polymerization.

The present invention may be embodied in other specific forms withoutdeparting from its spirit or essential characteristics. The describedimplementations are to be considered in all respects only asillustrative and not restrictive. The scope of the invention is,therefore, indicated by the appended claims rather than by the foregoingdescription. All changes which come within the meaning and range ofequivalency of the claims are to be embraced within their scope.

What is claimed is:
 1. A method of removing a dental adhesive,comprising: locating the position of the dental adhesive; directingradiant energy from a 405 nm diode laser into the dental adhesiveheating a violet light absorbing dye and causing the dental adhesive toweaken a bond formed with the dental adhesive; and breaking the bond byapplying a suitable force to overcome the weakened bond.
 2. The methodof claim 1, wherein directing radiant energy from a laser into thedental adhesive comprises directing radiant energy onto a dye orpigment.
 3. The method of claim 2, wherein directing radiant energy ontothe dye or pigment comprises directing radiant onto at least one of awhite dye, a white pigment, a translucent dye, and a translucentpigment.
 4. The method of claim 2, wherein directing radiant energy ontothe dye or pigment comprises directing radiant onto at least one of4,4″-(1,2-ethenediyl)bis-1,1′-biphenyl, and 4,4″-bis[(2-butyloctyl)oxy]-1,1′:4′,1″:4″,1′″-quaterphenyl and 2-[1,1′-biphenyl]-4-yl-6-phenyl-benzoxazole and3,5,3′″″,5′″″-tetra-t-butyl-p-sexiphenyl and2-(1-naphthyl)-5-phenyl-oxazole and 3,5,3 . . . ,5 . ..-tetra-t-butyl-p-quinquephenyl.
 5. The method of claim 2, whereindirecting radiant energy onto the dye or pigment comprises directingradiant onto at least one of a yellow dye and a yellow pigment.
 6. Themethod of claim 2, wherein directing radiant energy onto the dye orpigment comprises directing radiant onto2,2″-([1,1′-biphenyl]-4.4′-diyldi-2,1-ethenediyl)bis-benzenexulfonicacid disodium salt.
 7. A dental adhesive, comprising: a polymer; and aviolet light absorbing dye or pigment; and wherein the dental adhesiveis formulated to cure to form a bond that is weakened in response to thedye or pigment absorbing radiant energy from a 405 nm diode lasersubsequent to curing.
 8. The dental adhesive of claim 7, wherein the dyeor pigment comprises at least one of a white dye, a white pigment, atranslucent dye, and a translucent pigment.
 9. The dental adhesive ofclaim 7, wherein the dye or pigment comprises at least one of4,4″-(1,2-ethenediyl)bis-1,1′-biphenyl, and4,4′″-bis[(2butyloctyl)oxy]-1,1′:4′,1″:4″,1′″- quaterphenyl and 2-[1,1′-biphenyl]-4-yl-6-phenyl-benzoxazole and3,5,3′″″,5′″″-tetra-t-butyl-p-sexiphenyl and2-(1-naphthyl)-5-phenyl-oxazole and 3,5,3 . . . ,5 . ..-tetra-t-butyl-p-quinquephenyl.
 10. The dental adhesive of claim 7,wherein the dye or pigment comprises at least one of a yellow dye and ayellow pigment.
 11. The dental adhesive of claim 7, wherein the dye orpigment comprises 2,2″-([1,1′-biphenyl]-4.4′-diyldi-2,1-ethenediyl)bis-benzenesulfonic aciddisodium salt.
 12. The dental adhesive of claim 7, wherein the polymercomprises at least one of an acrylic and a methacrylic.
 13. The dentaladhesive of claim 7, wherein the polymer comprises at least one ofpolyethylene glycol methacrylates, polypropylene glycol methacrylates,Diurethane dimethacrylate, hydroxyethyl methacrylate, bis-phenol Adiglycidyl dimethacrylate, triethylenegycol dimethacrylate, isodecylmethacrylate, Bisphenol A ethoxylate dimethacrylates, and Poly(ethyleneglycol) methyl ether methacrylate.